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Oxide-based materials are promising candidates for use in high temperature thermoelectric generators. While their thermoelectric performance is inferior to commonly used thermoelectrics, oxides are environmentally friendly and cost-effective. In this study, Cu-based delafossites (CuFeO₂), a material class with promising thermoelectric properties at high temperatures, were investigated. This work focuses on the phase stability of CuFeO₂ with respect to the temperature and the oxygen partial pressure. For this reason, classical material characterization methods, such as scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction, were combined in order to elucidate the phase composition of delafossites at 900 °C at various oxygen partial pressures. The experimentally obtained results are supported by the theoretical calculation of the Ellingham diagram of the copper⁻oxygen system. In addition, hot-stage X-ray diffraction and long-term annealing tests of CuFeO₂ were performed in order to obtain a holistic review of the phase stability of delafossites at high temperatures and varying oxygen partial pressure. The results support the thermoelectric measurements in previous publications and provide a process window for the use of CuFeO₂ in thermoelectric generators.

Effect of Oxygen Partial Pressure on the Phase Stability of Copper–Iron Delafossites at Elevated Temperatures